US4725638A - Flame retardant polymer compositions - Google Patents

Flame retardant polymer compositions Download PDF

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Publication number
US4725638A
US4725638A US06/906,537 US90653786A US4725638A US 4725638 A US4725638 A US 4725638A US 90653786 A US90653786 A US 90653786A US 4725638 A US4725638 A US 4725638A
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Prior art keywords
flame retardant
polymer compositions
tbdpe
compositions according
retardant polymer
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US06/906,537
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Inventor
Eva Ellmann
Shaul Yanai
Pierre Georlette
Avraham Teurestein
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Bromine Compounds Ltd
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Bromine Compounds Ltd
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Assigned to BROMINE COMPOUNDS LTD., A CORP. OF ISRAEL reassignment BROMINE COMPOUNDS LTD., A CORP. OF ISRAEL ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: ELLMAN, EVA, GEORLETTE, PIERRE, TEURESTEIN, AVRAHAM, YANAI, SHAUL
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters

Definitions

  • the present invention relates to flame retardant polymer compositions. More particularly, the invention relates to flame retardant polymer compositions containing a versatile solid flame retardant agent.
  • halogen-containing compounds are frequently utilized with polymers, the flame retardant property being imparted by the halogen present therein.
  • a large number of different compositions are known for rendering polymers inflammable or self-extinguishing, such compositions being based generally on the use of various halogenated compounds.
  • certain bromine compositions are more effective flame retardant agents than the corresponding chlorine compounds.
  • Another important property required for flame retardant polymer compositions is the thermal stability.
  • An efficient flame retardant agent should also possess good thermal stability.
  • the invention consists of flame retardant polymer compositions comprising a readily flammable polymer selected from the group consisting of polyolefin, polyester, polyamide styrenics or polyurethanes and an amount of between 1% to 40% by weight of tetrabromodipentaerythirtol.
  • TBDPE Tetrabromodipentaerythritol
  • TBDPE has the highest bromine content, compared with its esters (63% versus 53% and 37% respectively). Compared with the diacetate ester, which has a closer bromine content, it has a much better thermal stability.
  • TBDPE has an improved effect on the melt flow index of polymers, by reducing its viscosity and thus enabling their easy processability. This is quite unexpected in view of the negative effect, i.e. increase in viscosity, imparted to polymers by well-known flame retardant agents.
  • Table 2 are summarized some comparative results concerning melt flow index and flame retardant property imparted by TBDPE (according to the present invention) and a known flame retardant such as Deca to high-impact polystyrene (HIPS).
  • melt flow index of HIPS alone is 4.4; by incorporation of 15 parts of TBDPE the MFI increases to 7.5 g/10 min, while by incorporating of 17.74 parts Deca, the MFI decreases to 3.6 g/10 min.
  • TBDPE can be easily obtained from dipentaerythritol and hydrogen bromide.
  • Example presented below being considered only a feasible approach.
  • gaseous HBr was bubbled until the temperature of the solution reached 50 degrees centigrade.
  • 381 g of dipentaerythritol were introduced at a rate such that the temperature did not exceed 65 degrees centigrade.
  • gaseous HBr was further bubbled with heating until the temperature reached 125 degrees centigrade and no more HBr was consumed.
  • the solution was cooled to 70 degrees C. and was then distilled in vacuum (60 mmHg) until the temperature in the flask increased to 115-120 degrees centigrade.
  • the flask was cooled to 60 degrees centigrade, and 350 ml of methanol was added followed by about 20 g of gaseous HBr. The mixture was heated under reflux for about one hour. Then, vacuum was applied (100 mmHg) and the mixture was distilled under vacuum until the temperature in the flask was about 115-120 degrees centigrade.
  • the off-white product was dried in an oven to a constant weight. An average yield of 80% was obtained.
  • the flame retardant according to the present invention is characterized by its outstanding stability against Ultraviolet radiation, while this a well known disadvantage of Deca.
  • the superior thermal aging behaviour imparted by the TBDPE to polypropylene is illustrated in Table 4.
  • Table 4 The results obtained with other flame retardant agents are also presented.
  • the compositions tested contained 1% of a masterbatch consisting of low density polyethylene+carbon black.
  • TBDPE flame retardant polymer
  • thermal stability Another important property for flame retardant polymer is the thermal stability. This property is imparted to a certain extent by the flame retardant agent. It was unexpectedly found that TBDPE possesses indeed improved thermal stability. The outstanding thermal stability of TBDPE is illustrated in a clear manner from the attached FIG. 1, wherein the graph of the thermal gravimetric analyses for TBDPE is presented along with some bromine-containing compounds related to TBDPE. It clearly appears from the weight loss percentage, versus the temperature, that TBDPE is the most stable: at 300 degrees C. its decomposition was only 15% whereas the other reagents were completely decomposed much before this temperature.
  • the flame retardant agent according to the present invention was also found to possess a particular advantageous property of non blooming in the polymer compositions. As known, blooming is considered a serious drawback which appears with additives for plastics, as a result of their poor solubility in the polymer.
  • Table 5 are presented the results of blooming tests carried out on polypropylene with TBDPE and for comparison with other three well known flame retardants: BN-451, Nonnen-52 and FR-930. The formulations tested were based on polypropylene (produced by Amoco) the flame retardant level in all formulations corresponding to 4% bromine, all formulations resulting in UL-94 V-2 rates.
  • the TBDPE agent according to the present invention was found to impart outstanding flame retardant property to ABS resin.
  • Table 6 are presented the results obtained with two levels of the agent: 15 parts and 24.7 parts (per 100 parts resin). For comparison purposes are given also results without the flame retardant agent.
  • the amount of TBDPE agent found to impart flame retardancy to the flammable polymer is in the range of 1 to 40 parts by weight of the polymer and most preferably in the range of 4 to 25 parts by weight of the polymer.
  • the flame retardant polymer compositions according to the present invention are fairly efficient, one may still enhance their effectiveness by including one or more synergistic compounds as known in the art, such as known metal compounds synergists conventionally used with flame retardants.
  • synergist compounds include oxides, sulfides or organic acid salts of antimony, arsenic or bismuth.
  • the preferred synergist compound for use in the compositions of the present invention is antimony oxide.
  • the amount of the TBDPE reagent and antimony oxide to be incorporated in the polymer compositions, in order to impart the required result, may be selected in a broad range depending on the particular polymer and the desired flame retardancy property to be imparted to the polymer composition.
  • the ratio between the flame retardant and antimony oxide is in the range of between 1 to 10 parts by weight and preferably between 2 to 5 parts by weight.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)
US06/906,537 1985-09-20 1986-09-12 Flame retardant polymer compositions Expired - Fee Related US4725638A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IL76434 1985-09-20
IL76434A IL76434A0 (en) 1985-09-20 1985-09-20 Flame retardant polymer compositions

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US4725638A true US4725638A (en) 1988-02-16

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US (1) US4725638A (US06312121-20011106-C00033.png)
JP (1) JPH0686546B2 (US06312121-20011106-C00033.png)
KR (1) KR870003163A (US06312121-20011106-C00033.png)
BE (1) BE905435A (US06312121-20011106-C00033.png)
BR (1) BR8604454A (US06312121-20011106-C00033.png)
CA (1) CA1284244C (US06312121-20011106-C00033.png)
CH (1) CH669602A5 (US06312121-20011106-C00033.png)
DE (1) DE3631292A1 (US06312121-20011106-C00033.png)
ES (1) ES2001692A6 (US06312121-20011106-C00033.png)
FR (1) FR2587712B1 (US06312121-20011106-C00033.png)
GB (1) GB2180541B (US06312121-20011106-C00033.png)
IL (1) IL76434A0 (US06312121-20011106-C00033.png)
IT (1) IT1197822B (US06312121-20011106-C00033.png)
NL (1) NL8602359A (US06312121-20011106-C00033.png)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4898900A (en) * 1987-12-28 1990-02-06 Bromine Compounds Ltd. 3,3-oxy-bis{[2,2'-di(bromomethyl)]}propanoic acid derivatives
US5104604A (en) * 1989-10-05 1992-04-14 Dexter Electronic Materials Div. Of Dexter Corp. Flame retardant epoxy molding compound, method and encapsulated device method of encapsulating a semiconductor device with a flame retardant epoxy molding compound
US5476716A (en) * 1988-10-17 1995-12-19 The Dexter Corporation Flame retardant epoxy molding compound, method and encapsulated device
WO1997042146A1 (en) * 1996-05-03 1997-11-13 Betzdearborn Inc. Methods for inhibiting the polymerization of ethylenically unsaturated monomers
CN103881375A (zh) * 2014-03-21 2014-06-25 滁州市永通交通设备有限公司 一种铁道客车尼龙软管

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607953A (en) * 1969-04-07 1971-09-21 Marathon Oil Co Process for production of 2,2-bis(halomethyl)-1,3-propanediol from pentaerythritol
US3700625A (en) * 1971-08-30 1972-10-24 Phillips Petroleum Co Flame-retarded olefin polymers and additive systems therefor
US3700957A (en) * 1971-01-13 1972-10-24 Grace W R & Co Flame retardant polyester plasticizer containing 2,2-dibromomethylene-1,3-propanediol
US3864306A (en) * 1970-06-19 1975-02-04 Hercules Inc Esters of brominated dipentaerythritol and polymeric compositions containing same
US3876509A (en) * 1971-08-04 1975-04-08 Dow Chemical Co Azeotropically removing hbr from brominated pentaerythritols and reacting with an epoxy
US3883581A (en) * 1973-05-23 1975-05-13 Dow Chemical Co Preparation of brominated pentaerythritols and esters utilizing certain dibasic acids
US3932541A (en) * 1971-08-12 1976-01-13 The Dow Chemical Company Process for the preparation of brominated pentaerythritols
US3951894A (en) * 1974-10-17 1976-04-20 Uniroyal Inc. Ternary flame-retarded compositions including iron compound
US4001182A (en) * 1972-03-20 1977-01-04 Phillips Petroleum Company Flame retardants for polymers
US4378440A (en) * 1977-12-09 1983-03-29 Labofina, S.A. Self-extinguishing polystyrenic compositions and process for their preparation

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607953A (en) * 1969-04-07 1971-09-21 Marathon Oil Co Process for production of 2,2-bis(halomethyl)-1,3-propanediol from pentaerythritol
US3864306A (en) * 1970-06-19 1975-02-04 Hercules Inc Esters of brominated dipentaerythritol and polymeric compositions containing same
US3700957A (en) * 1971-01-13 1972-10-24 Grace W R & Co Flame retardant polyester plasticizer containing 2,2-dibromomethylene-1,3-propanediol
US3876509A (en) * 1971-08-04 1975-04-08 Dow Chemical Co Azeotropically removing hbr from brominated pentaerythritols and reacting with an epoxy
US3932541A (en) * 1971-08-12 1976-01-13 The Dow Chemical Company Process for the preparation of brominated pentaerythritols
US3700625A (en) * 1971-08-30 1972-10-24 Phillips Petroleum Co Flame-retarded olefin polymers and additive systems therefor
US4001182A (en) * 1972-03-20 1977-01-04 Phillips Petroleum Company Flame retardants for polymers
US3883581A (en) * 1973-05-23 1975-05-13 Dow Chemical Co Preparation of brominated pentaerythritols and esters utilizing certain dibasic acids
US3951894A (en) * 1974-10-17 1976-04-20 Uniroyal Inc. Ternary flame-retarded compositions including iron compound
US4378440A (en) * 1977-12-09 1983-03-29 Labofina, S.A. Self-extinguishing polystyrenic compositions and process for their preparation

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4898900A (en) * 1987-12-28 1990-02-06 Bromine Compounds Ltd. 3,3-oxy-bis{[2,2'-di(bromomethyl)]}propanoic acid derivatives
US5476716A (en) * 1988-10-17 1995-12-19 The Dexter Corporation Flame retardant epoxy molding compound, method and encapsulated device
US5104604A (en) * 1989-10-05 1992-04-14 Dexter Electronic Materials Div. Of Dexter Corp. Flame retardant epoxy molding compound, method and encapsulated device method of encapsulating a semiconductor device with a flame retardant epoxy molding compound
WO1997042146A1 (en) * 1996-05-03 1997-11-13 Betzdearborn Inc. Methods for inhibiting the polymerization of ethylenically unsaturated monomers
CN103881375A (zh) * 2014-03-21 2014-06-25 滁州市永通交通设备有限公司 一种铁道客车尼龙软管

Also Published As

Publication number Publication date
IT8621770A0 (it) 1986-09-19
GB8622184D0 (en) 1986-10-22
DE3631292A1 (de) 1987-04-02
FR2587712A1 (fr) 1987-03-27
IL76434A0 (en) 1986-01-31
NL8602359A (nl) 1987-04-16
BR8604454A (pt) 1987-05-19
JPH0686546B2 (ja) 1994-11-02
GB2180541A (en) 1987-04-01
JPS6322863A (ja) 1988-01-30
KR870003163A (ko) 1987-04-15
CH669602A5 (US06312121-20011106-C00033.png) 1989-03-31
ES2001692A6 (es) 1988-06-01
GB2180541B (en) 1989-09-06
CA1284244C (en) 1991-05-14
IT8621770A1 (it) 1988-03-19
BE905435A (fr) 1986-12-31
FR2587712B1 (fr) 1989-06-09
IT1197822B (it) 1988-12-06

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Owner name: BROMINE COMPOUNDS LTD., P.O. BOX 180, BEER-SHEVA 8

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:ELLMAN, EVA;YANAI, SHAUL;GEORLETTE, PIERRE;AND OTHERS;REEL/FRAME:004765/0985

Effective date: 19860722

Owner name: BROMINE COMPOUNDS LTD., A CORP. OF ISRAEL,ISRAEL

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Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362